Catalyzed hydrocarbon reaction



-Patcnted Nov`.3, 1942 A 'y L' ca'rALYzED 2,301.04( u Y, y mnocxnsos arzAcTroNl Llewellyn eard; Hammond, ind., `and .Alex GQ I Oblad, Chicagmlll., assignorsto Standard Oil I Company, Chicago,`l1l., a corporation ot Indiana Application September 13, 1939, Serial No. 294,780 I s claims. (or 19e-so) invention relates to the manufacture of high knock rating` motor` fuels and in particular tothe conversion of petroleum naphthas of low .knock rating into gasoline having a high content of aromatic hydrocarbons.- p i p It is an object o! our process to produce arodehydroaromatization. Another object of the invention is toproduce gasoline o"f high `knock rating suitable for high compression engines by conductingthe vapors of petroleum" naphthas fcontaininga large lamount of openchain fand other aliphatic hydrocarbons into contact with an 'aromatizing catalyst `at 1a high temperature jiu thepresence of hydrogen for a sufficient `time from the catalyst zone are recycled externally 'and also through an externalheater, if desired.

Referring to the drawing, Figure 1, icedV stock which is preferably a naphtha fraction consisting principally of'hydrocarbons having from 6 `to 12 carbonatoms is introduced by line 'I0 into heater matic hydrocarbons from aliphatic hydrocarbons in a single catalytic operation which we term` "II `where it isheated to a conversion temperature of about 850-to 1000""11. or 1100? F. and preferably 875 to 1025 F. 'Ihe `naphthavapors are conducted by line `I2 into reactionchamber .I3 within which is located catalyst container I 4., 4

The naphtha vapors enter the catalyst container 'di contact to permit substantial conversion of-the open-chain hydrocarbons into aromatic hydrocarbons with eliminationoi hydrogen. vNaphthenic hydrocarbons are also convertedto` aro` matics by our process. 3A more speciiic object of the ,invention is to produce high knock rating gasoline'by recycling a substantialportidn of the Vreunion products resulting from this type of ifegulated; more vuniformly than is possible ,with-Z out recycling.

Si 3. The recycled products maybe heated before teintroducing intogthe catalyst zone thereby cornpensating for lossfoi heat from the endothermic reaction.

, 4'. The velocity of the gases and vapors passing through the catalyst zone is increased thereby resulting in a more rapid equilibrium between the vapor and gas stream and the conversion products on the surface oi the catalyst with the result that extreme conversion of hydrocarbons, for lexample, degradation to carbon and hydrogen, is avoided. p I

L 5. Superactive catalyst centers are partially deactivated by adsorption o'frecycled highly aromatic products with the result that less degradation of theparamnic hydrocarbons takes place on `these centers. f The" inventionwill be described with the help of the accompanying drawing in which Figure l .shows in simple diagrammatic form an apparatus for carrying out the reactionin which allof the recycling of products occurswithin theconversion chamber. Figure 2 shows an alternative arrange- `Il through venturi I5 which isarranged to draw `in additional'vapors from the vapor space I6 and 'forcethe mixture of vapors through the catalyst n containerll. w

The' mixture of vapors passes down through the catalyst I1 in container I4 and through the perforated bottom I8 whence the vapors escape from the converter by line I! leading to fractionator 2li.` Of all the vapors passing through the catalyst, about to 95%, preferably 6 0 to 75%, may be recycled through the annular passage 2I lining the catalyst chamber I4. condensate which may form in chamber I3 is withdrawn by a drag line 22.

In fractionator 20 the desired gasoline is separated fromheavier` polymerization products and the gasoline vapors are conducted by line 23 to condenser 24 communicating with receiver 25,"the gasoline being withdrawn by line 20. Higher boiling products of the reaction are withdrawn from fractioriator 20 by line 21 and may ;be discharged from the system, or, ii desired, the heavier products may be recycled by line 20 back `to the heater I I for further decomposition.

At the start of the process it is often desirable to introduce through line 20 into heater II with the naphtha feed, a controlled amount of hydrogen `gas to facilitate the catalyst reaction and i build up" the desired concentrationof hydrogen hydrogen is not essential to the operation oi' the process, it isv important to 4have sufficient hydrogen present in the catalyst to maintain a high catalyst `activity and prevent accumulation `of carbonaceous materials on the catalyst. When vhydrogen is being introduced into the feed stock at IIJ, itis not so essential to maintain the high recycle ratio Within I3 as is otherwise the case.

ment according to which the reaction products Recycle ratios, expressed. as the `Weight fraction of recycled stock in the total f eed to the catalyst, may be about 0.5 to 0.95.

When the catalyst has become sufficiently deactivated to warrant it, the operation is suspended, preferably by diverting the hydrocarbon vapors to a secondalternative reaction chamber. Valves 30 and 3| are closed and hydrocarbons are swept out of the exit chamber by means of steam or other inert gas introduced through line 32, passing out through line 33. Heated air or other oxidizing gas of controlled oxygen concentration is then introduced through line 32 and passes through the catalyst bed in container I4, the waste gases flowing out through line 33. The amount of oxygen in the oxidizing gas is controlled to prevent excessive heating of the catalyst from the combustion of carbonaceous materials therein. It is usually desirable that the temperature of the catalyst be kept below 1100 F. Inn the case of certain catalysts, however, it is possible to regenerate them at ternperatures as high as 1500 F. without serious loss in catalytic activity. During the regeneration operation, it is desirable to employ the same Venturi effect for recycling gases within the chamber I3,' thereby assisting theV temperature control. Recycling spent regenerating gases in this manner also assists in controlling the temperature of the catalyst mass. Pressures from atmospheric up to 100 pounds per square inch or more may be used inthe regeneration step.

` In the hydrocarbon conversion operation, it is desirable to employ pressures within the catalyst chamber of about 30 to 250 pounds per square inch, although pressures as high as 450 pounds per square inch may be used successfully. Still higher pressures than these are definitely undesirable as they result in consumption of hydrogen, in decrease of aromatization and the formation of hydrocarbons having low knock rating. The catalysts employed are preferably granular solid materials which adapt themselves to packingloosely within the catalyst container I4 to provide a porous bed. The preferred catalysts are oxides f the metals found in the left columns of groups IV, V and VI of the periodic system. Examples of such compounds are chromium, molybdenum, and tungsten oxides, vanadiumA oxide, and titanium, cerium and thorium oxides. These oxides may suitably be deposited on a bauxite or alumina'Y support, for example, by impregnating the granular alumina with a salt of the metal, such as the nitrate, and subsequently converting it to the oxide. Chromium nitrate may thus be deposited on alumina or in another example, ammonium molybdate or chromate may be deposited on alumina and thereafter'subjected to heating to convert the salt to the desired oxide.

The rate of passing the fresh naphtha feed into the catalyst `bed is preferably controlled Within the limits of about 0.1 or 0.2 to 25, preferably 0.5 to 2 0 time factor, the time factor being the hours required to pass a unit volume of liquid naphtha feed through a unit volume of gross catalyst space. A time factor of about 1 is generally satisfactory.

Referring now to Figure 2, hydrocarbon feed stock comprising gasoline or naphtha, for example, a midcontinent heavy naphtha boiling within the range of 250 to 425 F., is introduced by line 40 to pipe furnace 4l. The naphtha is vaporized and heated to a high temperature in coil 42Y and then passes Yby transfer line 43'to catalyst chamber 44.. The hot vapors may be below inclined bailles 45 thus providing more l uniform contact with the granular solid catalyst. The catalyst which has been previously described may suitably be in the form of granules of about 10 to 50 mesh and the tempera.- ture of th'e catalyst may be regulated within the range previously set forth, i. e., about 875 to 1025 Hydrogen maybe added to the hydrocarbon stream by line 46 when desired.

The vaporous products leave the catalyst chamber by line 41 and are conducted to fractionator 48 where they are separated into an overhead gasoline fraction, withdrawn by line 49, and a heavier than gasoline fraction, withdrawn by line 50. The gasoline fraction may be condensed in condenser 5I and separated by separator 52 and gasoline discharge line 52a. Fixed gases are conducted from the system by vent 53 or recycled to the system by line 54. Gases thus recycled, consisting essentially of hydrogen and hydrocarbon gases includingy methane, ethane, ethylene, propane and propylene, may be introduced into the hydrocarbon feed by line 40. When recycling these hydrogen-containing gases, we may avoid adding fresh hydrogen by line 46.

A substantial portion of the hot vapors leaving chamber 44 by line 41 is recycled by line 55, blowerSS, and line 51 back to the catalyst chamber 44 into which it may be introduced by one or more communicating lines 51a, 51h and 51e. The amount of reaction products thus recycled may suitably be about 1 to 4 times the amount of fresh hydrocarbons introduced to the catalyst by line 43. We may also recycle the reaction products to line 58 and heater 59 wherein the products may be heated to a temperature somewhat higher, for example, 25 to 100 F. above that employed in the catalyst chamber 44. In this maner we may maintain the desired reaction temperature in catalyst chamber 44 without the application of indirect heating or the necessity of preheating the feed stock in heater 4| to an excessive temperature Where undesirable thermal cracking becomes extensive. Thus where it is desired to maintain the catalyst in chamber 44 at a temperature of 950 F., we may heat the recycle vapors to the temperature of 975 F. and also introduce the naphtha vapors from heater 4l at this same temperature, thus .providing 2 5 degrees of superheat to compensate for loss of temperature during the catalytic reaction. Y tx.

Instead of employing a separate heater 59 for heating recycle products, we may recycle these products through valved line 60 directly to the naphtha heater 4l and in this case We prefer to introduce the recycled products into coil 42 at an intermediate point thereof where the temperature of the coil is substantially that of the products recycled. The catalyst in 44 may be arranged either in a fixed bed as shown or in a moving bed. In a moving bed, means are provided at the top and the bottom of the catalyst chamber 44 to continuously or intermittently introduce and discharge the granular catalyst as it becomes spent in the operation. This involves the use of valve sealing means to admit and remove catalyst and to prevent escape of the vapors from the catalyst chamber. Where a moving bed catalyst is employed, regeneration of the catalyst may be effected in auxiliary equipment, whereas in the case of a fixed bed catalyst, regeneration is more conveniently carure2.

yaziona ricd out in catalyst when spent is sublected to the action of an oxidizing, gas as previously by means not shown in tha from a` paramnic type crude o il. `Naphtha of boiling range`175 to 450v suitable, although we usually prefer to treat a naphtha fraction of somewhat narrower range, e. g., 300 to i t As previously indicated,` in the aromatization'of 450 F. Somewhat heavier distillates maybe emnaphthas by catalysts, it'isA important to mainployed, for example, distillates boiling up to 525 tain a desired hydrogen concentration in the P.. but if thestock is too heavy, dimculty will be catalyst in order tominimize carbonization ofthe encountered with carbonization and e excessive catalyst which would result from hydrogen de` catalyst deactivation resulting in uneconomically flciency. At the same time, it is important to l short runs between regeneration cycles.

` avoid excessive hydrogen partial pressure such Although we have described our invention with as that employed in typical high pressure hydrorespect to specific embodiments thereof, we in- `genation reactions where hydrogen pressures of tend that it be limited only by the following 1000 to 4000 lbs. per square inch are commonly claims. 'e used. In our process the recycled products con- We claim: tain sumcient hydrogen to prevent undesirable 1. In the process of converting petroleum t carbon deposition and deactivation of the catanaphthas of low knock rating to aromatic motor lyst. Thus, the hydrogen in the recycled prodfuels of high knock rating wherein the vapors of ucts may be about 40 to 80%, based on the fixed said naphthas are continuously contacted with'a vmgases present. In the case of fresh catalyst, the solid aromatizing catalyst at a`high conversionl hydrogen concentration of the gas produced in temperature and in the presence of hydrogen, the ithe process will be considerably higher than after improvement comprising regulating the condithe catalyst has become partially spent. This tions of temperature, pressure and time of coneiiect is apparently due to the diminishing detact to produce asubstantial amount of hydrogen hydrogenation activity of the catalyst which perin the reaction products directly recycling in conmits cracking reactions producing methane and tact with said catalyst, without fractionation or other fixed gases to become more predominant. substantial cooling, a portion of the reaction The life of a catalyst in this operation will vary products constituting about i to 4 times the considerably, depending upon the stock used as amount of fresh naphtha charged to the catalyst well as the catalyst employed. With a typical and continuously withdrawing a portionof the chromium oxide on alumina catalyst, the life of reaction products and recovering gasoline therethe catalyst may be about 10` to 20 hours after from. e which regeneration is required. 2. In the process of converting petroleum It should be understood that our process is naphthas of low knock rating to aromatic motor strictly a dehydrogenation process and not a hyn fuels of high knock rating wherein the vapors of drogenation process inasmuch as there is `an said naphthas are continuously contacted with a overall net production of hydrogen. That is, solid aromatizing catalyst at a high conversion even though some hydrogen be added at 46, the temperature and in the presence of hydrogen, the

amount of hydrogen discharged in the gases at 53 a Y improvement comprising regulating the condiis larger. If a portion of the gases produced in tions of temperature, pressure and time of con- `the process be stored, it may be used at the betact to produce a substantial amount of hydrogen ginning o f each succeeding run with fresh catain the reaction products, directly recycling in lyst, thus-fehtirely avoiding the need for fresh contact with said catalyst, Without fractionation hydrogen. Once the catalytic aromatizing reor substantial cooling, a portion of the reaction action has become established, suiiicient hydroproducts constituting a fraction by weight of gen will be obtained from the gases recycled by about 0.5 to 0.95 of -the total stock charged to the line 55. catalyst,- and continuously withdrawing a portion When recycling reaction products through line of the reaction products and recovering the gaso- 58 or line 60 and heaters 59 and 4i respectively, line products therefrom. thj amount of heat transferred by the gas per 3. 'I'he process of converting open-chain hyunit volume of gas recycled is far greater than drocarbons into aromatic hydrocarbons suitable would be the case if hydrogen only were recycled. for antiknock motor fuel, comprising heating a This results from the higher heat capacity of the suitable naphtha containing said open-chain hyreaction products and facilitates the maintedrocarbons to a high temperature above 875 F., nance of the desired reaction temperature in cataforcing the resulting `hydrocarbon vapors under lyst chamber 44.. The higher velocity of the pressure through an aspirating means and a vapor stream passing through the catalyst is also porous bed of aromatizing catalyst, supplying the conducive to more rapid establishment of equilibreaction products from said aromatizing catalystv riurn between the hydrocarbons adsorbed on the to said aspirating means, whereby a substantial surface of the catalyst and the hydrocarbons in portion of said `products is resubjected to the the vapor stream with the result that a more seaction of said catalyst, said portion correspondlective catalytic reaction takes place than in the ing to a ratio of about 0.5 to`0.95 recycled stock to case where no recycling of lproductsds practiced. total feed, withdrawing the remainder of said ree More effective maintenance of catalyst activity action products and separating therefrom the is also obtained by use of the higher vapor velocidesired motor fuel fraction. ties. Typical of 'the results which may be ob- 4. In the process of converting open-chain hytained by our process, we may charge an East drocarbons into aromatic hydrocarbons wherein Texas heavy naphtha of about 40 octane number open-chain hydrocarbons having 6 or more carand produce an aromatic gasoline of l'75 to '85 bon'atoms are subjected in a continuous stream octane number, C. F. R. motor method. The to the action of a solid aromatizing catalyst and concentration of aromatic hydrocarbons includwherein the catalyst is disposed in the form of ing benzene, toluene, xylene, ethyl benzene, etc. granules in a stationary bed in an elongated unmay be about 30 to 60% of the product. As preheated passage and the temperature of the cataviously indicated, we prefer'to process a heavy lyst tends to become successively lower throughnaphtha fraction of petroleum, preferably naphout said passage because of the endothermic of said open chain hydrocarbon stock charted.

5. The process of claim 4 wherein the recycled reaction products are introduced into said catalyst passage at l. succession of spaced points.

6. The process of clnim 4 wherein the solid sromatizing catalyst employed'comprises an oxide of l. metal oi the lett column o! group VI ot the periodic system.

ALEX G. OBLAD. 

